Quaternary salts of triazene azo dyestuffs



United States Patent 3,290,280 QUATERNARY SALTS 0F TRIAZENE AZO DYESTUFFS Jacques Voltz, Basel, and Werner Bossard, Riehen, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed Aug. 2,1963, Ser. No. 299,477

Claims priority, application Switzerland, Aug. 15, 1962,

6 Claims. (Cl. 260140) formula AN=NB-NH (I) R represents a low alkyl radical and n represents 0 or 1,

to form a compound of formula (oH=oH 1 2 a R-N C=N-N=N-BN=NA wherein A and B have the meanings given in Formula I and X, R and n have the meanings given in Formula II,

and

(b) Converting the respective compounds of Formula III by reaction with an ester of a lower alkanol and a strong acid into a water soluble quaternary color salt of a structure defined within the resonance Formulas Na and IV]; below I of which the latter type only is used hereinafter and in the appended claims to define said structure. In Formulas IVa and IVb,

R represents a lower alkyl radical and Y represents an anion, and A and B have the meanings given in Formula I and X, R and n have the meanings given in Formula II.

In the Formulas I, III and IV, A and B advantageously represent a phenyl or 1,4-phenylene radical which is either unsubstituted or contains substituents which do not dissociate acid in water.

In those compounds according to the invention in which the nitrogen-containing ring in Formulas II, III and IV is five-membered, the divalent radical X is, for example, the 1,3-propenylene radical -CH=CH-CH the vinyl- Patented Dec. 6, 1966 amino radical CH=CHNH, the vinylthio radical CH CH-S-, the vinyloxy radical -CH=CH-O-, or the radicals -CH:N-NH, -N=CH-O-, N=CHS-, provided the index n is 0. When X has these meanings, it thus completes a pyrrole, pyrazole or imidazole, thiazole, oxazole, 1,2,4-triazole, 1,3,4-oxidazole or 1,3,4-thiadiazole ring.

In those cases in which X is an o-phenylimino an o-phenylthio radical or o-phenyloxy radical the hetero ring is an indazole or benzimidazole, benzthiazole or benzoxazole ring.

In those compounds according to the invention in which the nitrogen-containing ring in the formulas mentioned has six members, X is, for example, the butadienylene radical -CH=CHCH=CH, the styrylene radical bound in o-position to the vinyl group or the propenylimino radical CH=CH-CH:N-, provided it is 0.

In the compounds according to the invention in which the index n is l, X represents, for example, the vinylene or the o-phenylene radical. In these meanings in the first case X completes a pyridine or a quinoline ring bound in the 2-position with the triazene group or an isoquinoline ring bound in the 1-position and a pyrimidine ring bound in the 2-position and, in the second case, it completes a pyridine and quinoline ring bound to the triazene group in the 4-position.

Advantageously X represents the radical and n is 0, i.e. the nitrogen-containing heterocycle in Formulas II, III and 1V is a benzthiazole ring (or benzthiazoline ring) which may be substituted as defined.

As defined, the aromatic nuclei A and B can contain substit-u-ents which do not dissociate acid in water. The same is true of any aromatic nuclei present forming a component of X. Examples of substituents are: aliphatic, cycloa lip hatic, araliphatic or aromatic groups, in

particular lower alkyl groups such as the methyl or ethyl group, lower alkoxy, lower cycloal-koxy, aralkoxy, especially mononuclear carbocyclic-aryl lowe-r alkoxy, or a-ryloxy in particular mononuclear carbocyclic aIyloxy groups, principally the methoxy or ethoxy group, also the hydroxyl group, acylaimino, especially lower alkanoylamino groups such as the acetylamino group, or the benzoylamino group, arylamino, especially mononuclear carbocyclic arylamino groups such as the phenyla-mino group, halogens such as, especially, chlorine or bromine, the cyano, nitro or trifluoromethyl group, carboxylic acid and sulphonic acid amine groups (including those substituted at the amide nitrogen atom), carboxylic acid ester groups, especially lower alk-oxy carbonyl, sulphonic acid aryl ester groups, especially monouuclear carbocyclic aryloxy-sulfionyl, hydrocarbon sulfonyl groups, especially lower a'lkoxy sulfonyl, such as methylsulfonyl or ethyl- U sulfonyl, or phenylsulfony-l group etc. Advantageously B does not contain any substituents in the o-position to the aminoor triazene-group.

In Formulas II, III, IV, R and R represent, preferably a lower alkyl radical such as methyl, ethyl, n-propyl, isopropyl or n-butyl, particularly, however, methyl or ethyl.

Y in Formula IV is any anion desired, in particular a colourless tone, for example the anion of an inorganic acid such as a hydrohalic acid or sulfuric acid, unesterified or monoesterified with lower alkanols, the anion of perchloric acid or of an organic acid e.g. an arylsulfonic acid such as 'benzeneor p-toluene-sulfonic acid, or oxalic acid. The anion, however, can also be derived from inorganic complex acids such as zincor cadium-hydrohalic acid.

As amino compounds of Formula I, principally those of the 4-aminoazobenzene series but also those of the 3-aminoazobenzene series are used. The benzene nuclei can be further substituted asndefined, for example, by substituents of the type given above.

Imino heterocycles of Formula II to be coupled therewith are derived, for example, from the 5- 'and 6-membe-red rings mentioned in the definition of X and n, supra. These are, thus, 3-imino-pyrazoline, Z-imino-imidazoline, Z-imino-thiazoline, 2-imino-oxazoline, 3-imino-1,2,4-triazoline, Z-imino-1,3,4-oxdiazoline, 2-imino-1,3,4-thiadiazoline, Z-imino-benzthiazoline, 2-imino-benzimid'azoline, 3-imino-indaz'oline, 2-imino-dihydropyridine, 4-imino-dihydropyridine, 2 imino dihydroquinoline, 4-imino-dihydroquinoline, Z-imino-dihydropyrimidine or l-iminodihydroisoquinoline alkylated at a nitrogen atom in the heterocyclic ring; in one group of compounds according to the invention fused benzo rings in the above listed ring systems contain substituents of the type mentioned above. Preferred coupling components of Formula II are the 3- alkyl-2-imino benzothiazolines and their benzene ringsubstituted derivatives.

Coupling is performed in neutral or weakly alkaline aqueous medium; the triazene of Formula III precipitates in a form which can be easily filtered off.

Examples of esters of lower alkanols with strong acids, with which the triazene compounds of Formula III are reacted to form the colour salts of Formula IV are: methyl, ethyl, propyl or b-utyl chloride or the corresponding bromides or iodides, or methyl or ethyl benzene sulfonate or methyl or ethyl-p-toluene sulfon'ate and, in particular, dimethyl and diethyl sulfate.

The conversion of a triazene compound of Formula III into the corresponding quaternary color salt of Formula IV is advantageously performed with an excess of the alkylating agent and, advantageously, in an inert organic solvent, at a reaction temperature of about 80 to 150 C. *It is often necessary to perform this conversion under pressure. Suitable solvents are, for example, unsubstituted or halogenated and/ or nitrated aromatic, preferably mononuclear, hydrocarbons such as halogen benzenes or nitrobenzenes, unhalogen-ated or halogenated aliphatic hydrocarbons, especially halogenated lower alkanes or lower alkenes, e.g. trichloroethylene or tetrachloroethane, ketones, especially di-(lower alkyl)-ketones, such as methylethyl ketone or methylisopropyl ketone, or ethers such as dioxan.

'I he quaternary compounds of Formula IV are in the form of salts of the acid of the alkylating agent used for their production, i.e., for example, they are halides, methos-ulfates or ethosulfates. If desired, these can also be converted into salts of other acids by double decomposition reaction [Remy, Inorganic Chemistry, pp. 730- 31 1956)], for example, into oxalates, perohlo'rates or sulfates by the addition of aqeuous solutions of the alkali metal salts of oxalic acid or perchloric acid or sulfuric acid. Double salts can also be produced, for example, with the dyestulf halides and corresponding zinc or cadium salts.

A modification of the process for the production of triazene dyestuffs according to the invention consists in reacting, in the presence of alkali, one mol of a diazoamino compound of formula (CH=CH n C=NN=NBN=NA x (Va) the other resonance formula which is (OHGH)\,, N ONN=N-BN=NA x 1 1 (Vb) wherein A represents an aryl radical which may contain substituents which do not dissociate acid in water,

B represents an arylene radical which may contain substituents which do not dissociate acid in water,

X represents a divalent radical which completes the nitrogen-containing ring to a five or six membered ring, and

n represents 0 or 1,

with one mol of the ester of a low alkanol with 'a strong acid, to form a compound of Formula III and, if desired, converting this with at least one mol of a further ester of a low alkanol with a strong acid into a water soluble quaternary color salt of Formula IV.

Naturally, the remarks regarding A, B, X, n, R, R and Y in the first process also apply here.

The compounds of Formula V used as starting materials are obtained, for example, by coupling an aminoazo compound of Formula I with a nitrogen heterocyclic compound of the two resonance formulas The reaction of the compound of Formula V with the alkylating agent to form the triazene compound of Formula III is advantageously performed in an organic solvent such as aliphatic ketones, esters or ethers, e.g., in acetone, methylethyl ketone or diethylketone, in ethyl acetate or in dioxan. Suitable alkaline agents for the reaction are, e.g., the sodium or potassium salts of carbonic acid.

The conversion of the triazene compounds of Formula III into color salts of Formula IV has been discussed in the first process.

Color salts of Formula IV in which R and R are identical can also be obtained in one step by reacting the starting materials of Formula V with an excess of the ester used as alkylating agent, alone or in the presence of an organic solvent such as, e.g., a conventional ketone, ester or ether-type solvent. 1

A further modification of the process for the production of water soluble quaternary color salts of triazene compounds according to the invention consists in converting a compound of formula with the ester of .a low alkanol with a strong acid, to form a compound of Formula IV.

In this modification also, the remarks in the first process regarding the symbols A, B, X, n, R, R and Y apply.

The compounds of Formula VI used as starting materials for this process are obtained by coupling the diazonium compound of an amino-nitrogen heterocycle of the-formula (CHCH)n N C-NHz with an aminoazo compound of the formula A-N=NB-NH X, n, A, B and R having the meanings given above, in an aqueous medium in the presence of solubility promoters such as dimethyl formamide or acetic acid. The coupling can also be performed in an organic solvent such as in a ketone, ester or ether; preferred solvent is acetic acid.

The reaction of compounds of Formula VI with the esters used as alkylating agents to form the color salts of Formula 1V is performed analogously to the conversion of the triazene compounds of Formula III into these salts described in the first process.

The triazene compounds corresponding to Formula III are difficultly soluble in Water. They are suitable for the dyeing of hydrophobic organic fibers in aqueou dispersion, e.g., of cellulose dito tri-acetate fibers; particularly, however, they are suitable for dyeing of fibers consisting of polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols, for example of polyglycol terephthalates such as Terylene, Dacron, Tergal, or Trevira.

The dyestuffs can also be used, however, for the dyeing of synthetic polyamide fiber such as Nylon 6, Nylon 66 or Nylon 11.

The fibers consisting of polymeric ester compounds mentioned are dyed with aqueous dispersions of dyestuffs of Formula III according to the invention, for example, at the boiling point of the water in the presence of carriers such as phenylphenol, polychlorobenzene compounds or similar auxiliaries. Examples of dispersing agents for this purpose are, for example, polycondensation products of alkylene oxide with higher alkanols. The dyeing can also be performed, however, at higher temperatures above 100 C. under pressure. In individual cases, the drawing power of the dyest-ufls can be still further improved by mixing two or more triazene dyestuffs corresponding to Formula III according to the invention.

Yellow to orange dyeings are obtained on the textile material mentioned which have good wet and light fastness properties.

The water soluble color salts of Formula IV are highly suited for the dyeing of polymeric and copolymeric acrylonitrile fibers, especially in the form of polyacrylonitrile textile fabrics, in particular of acid-modified acrylic fibers, i.e. acrylic fibers having acid sites, for instance the sulfonate-modified acrylic fibers described in US. Patents 2,837,500 and 2,837,501 (Orlon) and in particular of Example 1 (A) A diazoniurn salt solution prepared in the usual way from 19.7 parts of 4-aminoazobenzene is poured with stirring into an acetic acid solution of 19.4 parts of 2,3-dihydro-2-imino-3-methyl-6-methoxy benzthiazole in 200 parts of ice water.

The pH of the reaction mixture is increased to 8 by the slow drop by drop addition of aqueous sodium hydroxide solution. After about 1 hour, coupling is complete. The resulting yellow dyestuff is filtered otf, washed neutral with water and dried in vacuo at 70. The product is a yellow powder and corresponds to the formula l CH3 OCH Dyestuffs having similar properties are obtained by 1 replacing in the above example, the 19:7 parts of the diazonium compound of 4-aminoazobenzene, by equivalent amounts of the diazoniurn compounds of 4-amino- 3,2-dimethylazobenzene, 4 amino-2-chloroazobenzene, 4-amino-3-chloroazobenzene, 4-amino 4-chloroazobenzene, 2 methyl 4 amino 2,4 dichloroazobenzene, 2-methoxy-4-amino-2',4' dichloroazobenzene, 2,2',4-trichloro-4-aminoazobenzene, 3-methoxy-4-amino-6-methy1- 4-chloroazobenzene, 3,6-dimethoxy-4-aminoazobenzene, 3,6-dimethoxy-4amino-4-ohloroazobenzene, 4-amino-2', 3',4-trichloroazobenzene, 2 4 methyl-4-arnino-2,3',4'trichloroazobenzene, 4 amino-4 bromoazobenzene, 2- methyl-4-arnino-4' bromoazobenzene or 2-methyl-4- amino-2'-trifluoromethylazolbenzene.

(B) 4.0 parts of the diazoimino compound so obtained is heated for 10 minutes at 100110 in 10 parts of dimethyl sulphate. The melt, while still warm, is taken up in 400 parts of 80-warm water, the solution is buffered with sodium acetate until it has an acetic acid reaction and, after adding a small amount of animal charcoal, it is filtered. With the aid of zinc chloride and sodium chloride, the orange color salt is precipitated as zinc chloride double salt of the formula on heating the open dyebath or in a closed dyebath under CH This basic dyestuff dyes potlyacrylonitrile fibers such as Orlon in yellow-orange shade from an acetic acid solution. The dyeings are distinguished by their excellent fastness to washing, steam and light.

69 OCH;

'3 are obtained by using equivalent amounts of the coupling products obtained as described above under (A) with the al-kyla-ting agent listed in the following table under R and the anion listed in column Y,

orange dyestufis having similar dyeing propenties are obtained.

(B) A mixture of 4.3 parts of the diazoi-mino compound obtained according to paragraph A and parts EX. No. B A

Alkylating agent 2-methylphenyl 2-chl0rophenyl 3-chlorophenyl 4-chloropheny1 Z-methyl-l,4-phenylene 2',4-dicl1lorophenyl Z-methoxy-lA-phenylene -do 2-ehloro-l,4-pheny1en Z-medthoXy-I ,4-phenylene o 2-methy1-1,4-phenylene 1,4-phenylene Z-methyl-l ,4-phenylen. 2-1nethyl-1,4-pl1enylene 2-trifiuoromethylphenyl Methyliodide in chloroform iethylsulfate imethylsulfate Cl- With NaCl Example 17 (A) A solution of 3.9 parts of sodium nitrite in 20 20 parts of water is poured, while stirring vigorously, into a fine suspension of 10.7 parts of 4-amino-4-hydroxyazobenzene in a mixture of 200 parts of water, 20 parts of concentrated hydrochloric acid and 0.1 part of a fatty alcohol/polyethylene oxide condensation product and the mass is kept for 1 hour at room temperature. Any excess nitrite present is decomposed by the addition of sulfainic acid. The clarified diazonium salt solution is poured into an acetic acid solution of 12.2 parts of 2- amino-3-ethyl-6-methoxybenzthiazolium chloride in 200 parts of water. The reaction mixture is neutralised by the dropwise addition of dilute sodium hydroxide soluof freshly distilled diethyl sulphate are heated to 120 within 10 minutes and kept at this temperature for a further 10 minutes. The still warm melt is worked up as described in paragraph B of Example 1. The orange color salt of the formula 0o1i-r ZnOl3 C2115 C2115 so obtained dyes polyacrylonitrile fibers from an acetic acid solution in orange shades. The bath is substantially exhausted. The dyeings have excellent fastness to Washing, steam and light.

On using dimethyl sulphate instead of diethyl sulphate, an orange colour salt is obtained which has similar dyeing properties.

Similar color salts are obtained by using equivalent amounts of coupling products obtained as described above under (A) with the alkylating agent listed in the following tron, whereupon the dyestufi" of the formula table under R and the anion listed in column Y;

Ex. B A Alkylating agent R Y No.

18 1,4-phenylene 3-hydroxyphcny1 Diethylsulfate C H5 Cl" with NaOl 19 do 4-methoxyphenyl Methyl bromide -CH Br 20.. 2-methyl-1,4-phenylene do Diethylsulfate CZH5 CzH5--SO4- 2-ohloro-l,4-phenyl do Dimethylsulfate CH ZnClr 1,4-phenylene 3-rnethoxypl1enyl Methyl-p-tosylate CH p-Tosylate do 2-methoxyphenyl Methyliodide (in chloroform) OH; I-

2,4-dimethoxyphenyl Diethyl sulfate -C H5 C H SO4- 2 ,5-dimethoxypheny do O2H C2H SO4- 2'-metl10xy-5methylphenyl do 0 H5 0 11 804- o 4-aoety1aminopl1enyl Dimethylsulfate. -CH ZnClr 2-n1ethy1-1,4-phenylene. 0 do OH CH3SOj Examples 29 to 37 lzHs precipitates. On completion of the coupling, the yellow diazoimino compound is filtered ofi, washed neutral with water and dried in vacuo at The product dyes polyester fibers made from poly'glyool terephthalate such as Trevira in pure yellow-orange shades from an aqueous dispersion.

By using in the above example, with otherwise the same procedure, instead of the 10.7 parts of 4-amino-4-hydroxyazobenzene the equivalent amounts of 4 amino 3' hydroxyazobenzene, 4 amino-4-methoxyazobenzene, Z-methyl 7 4 amino-4'-methoxyazobenzene, 2-chlotro-4- amino-4-methoxyiazobenzene, 4-amino-3methoxyazobenzene, 4 amino-2'-methoxyazobenzene-4-amino-2f-4'-dimethoxyazobenzene, 4 amino 2',5-dimethoxyazobenzene, 4-amino-2-methoxy 5 methylazobenzene, 4- amino 4' acetylaminoazobenzene, 2 methyl 4 amino 4' acetylaminoazobenzene, then other yellow- A solution of 3.9 parts of sodium nitrite in 20 parts of water is poured, while stirring vigorously, into a fine suspension of 10.7 parts of 4-amino-4'-hydroxyazobenzene in a mixture of 200 part-s of water, 20 parts of concentrated hydrochloric acid and 0.1 part of a fatty alcohol/ polyethylene oxide condensation product and the mass is kept for 1 hour at room temperature. Any excess nitrite present is decomposed by the addition of sulfonic acid.

By pouring in the clarified diazonium salt solution in to an acetic acid solution of the 2-amino-3-ethyl-6-methoxybenzthiazolium chloride used in Example 17, an acetic acid solution of 11.5 parts of 2-amino-3-methyl-6- methoxy-benzthiazolium chloride, 12.9 parts of 2-amino- 3-n-propyl-6-methoxybenzthiazolium chloride, 13.6 parts of Z-amino-3-n-butyl-6-methoxybenzthiazolium chloride, 14.4 parts of Z-amino 3 -carbomethoxymethyl-G-methoxybenzthiazolium chloride, 26.6 parts 2-amino-3-(N,N- dimethyl-carbamyl-methyl)-benzthiazolium chloride 25.6 parts 2-amino-3-(3-carbamylethyl)-benzthiazolium chloride, 15.1 parts of Z-amino-3-carbethoxymethyl-6-methoxybenzthiazolium chloride, 13.6 parts of Z-amino-B-carbamylmethyl 6 methoxybenzthiazolium chloride, 14.3 parts of 2 amino 3 methylcarbamylmethyl-6-methoxybenzthiazolium chloride, 15.1 parts of 2-amino-3-carbonethoXyethy1-6-metho-xybenzthiazolium chloride, 15.0 parts of 2-amino 3 methylcarbamoylmethyl-6-meth'oxybenzthiazolium chloride respectively there are obtained the yellow-orange cationic dyestuffs of the formula 10 no-3-methyl-(l,3,4)-thiadiazoliumor 2-amino-3,5-dimethyl-(1,3,4)-thiadiazolium-methosulphalte can be used and diazoimino compounds having similar properties are obtained.

(B) 7.3 parts of the diazoimino compound obtained according to paragraph A are heated for minutes at 110 with 3.0 parts of dimethyl sulphate in 250 parts of tetra- S a) chloroethane. To remove the organic solvent, 300 parts OCH3 of hot water are added and the reaction mixture is sub- AN=NBNN=N--C, e 10 jected to steam distillation. The aqueous solution of the t, Y dyestuff so obtained is clarified hot and the yellow-orange color salt is precipitated with the aid of zinc chloride and R sodium chloride. It has the formula /SCH 63 I znon CH3 BNCH listed in table.

Ex No. R A B Alkylating agent R Y 29 CH3- 4-hydroxyphenyl-. 1,4-phenylene dimethylsulfate CH3 CH3SO4 (1 do Methyliodide (in chloroform). CI-Is I -nC 4H9 Dimethylsulfate ZnClr -CH2COOCH3 Diethyl sulfate 02115804- CHzCOO-CzHs (lO CzHsSOr O H2-CON H2 Methylp-tosylate p Tosylate CHzCONH-CH3 ..d0 Do. C2H4COOCI-I3 d Methyl bromide Br- -C2H4CO-NHOH3. do do- Diethyl sulfate -o1H5 01- (with NaCl) Example 38 azonium salt solution is poured into the acetic acid solution of 11.3 parts of 2-amino-3-methyl-thiazolium methosulphate in 200 parts of water and the pH of the coupling mass is adjusted to '8 by the dropwise addition of dilute From an acetic acid bath, it dyes polyacrylonitrile fibers such as Dralon, in yellow-orange shades. The bath is substantially exhausted. The dyeings have very good Wet and light fastness properties.

Similar yellow cationic dyestulfs of the formula are obtained by using equivalent amounts of the coupling products obtained as above under (A) with the alkylating agent listed in the following table under R and the anion listed under Y, A and B being in all cases the same as in Example 38.

Ex. No. Z Alkylating agent R Y 39 3-methyli-methoxy-thiazolyl-(2) Diethylsulfate C2H C2H SO4- 40-.- 3,4-dimethylthiazolyl-(2). Dimethylsulfate CHa CHaSOr 42 3,4,5-trimethylthiazolyl-(2) Methylbromide CH;4 Br

43 3-methyl-4,fi-diphenylthiazolyl-(2).. Dimethylsulfate CH; Cl-(with NaCl) 44 3-methyl-1,3.4-thiadiazolyl-(2) Methyl-p-tosy1ate CH:; p-Tosylate 45 3,5-dimethyl-1,3,4-thiadiazolyl-(2) Diethylsulfate OZH 0111 804- sodium hydroxide solution. The yellow dyestuif of the formula SCH precipitates. On completion of the coupling, it is filtered oil, washed neutral With water and dried in vacuo at 60-70.

Similar yellow dyestuffs are obtained on using equivalent amounts of 2-amino-4-methyl-4-methoxythiazolium chloride (9.0 parts), 2-amino-3,4-dimethylthiazolium chloride (8.2 parts), 2-amino-3-ethyl-4-phenylthiazolium ethosulphate (16.5 parts), 2ramino-3,4,5-trimethylthiazolium chloride (8.9 parts) or 2-amino-3-methyl-4,5-diphenylthiazolium chloride (15.2 parts). Instead of Z-aminothiazole derivatives, also the corresponding amounts of 2-ami- Example 46 (A) A slurry of 13.3 parts of finely distributed 4-amino-4'-methylsulphonylazobenzene in a mixture of-2 00 parts of water, 20 parts of concentrated hydrochloric acid and 0.2 part of a fatty alcohol-polyethylene oxide condensation product is diazotised in the usual way by the addition dropwise of a solution of 3.9 parts of sodium nitrite in 20 parts of water. A solution of 9.9 parts of 2,3-dihydro- 2-imino-3-methyl-6-chloro-benzthiazole in 200 parts of 10% acetic acid is poured into the clarified solution of the diazonium salt so obtained and the pH of the coupling mass is adjusted to 8 by the addition of dilute sodium hydroxide solution. On completion of the coupling the yellow dyestuff is filtered oif, washed neutral with water and dried in vacuo at -70". The product has the formula yellow-orange shades.

12 The dyeings are distinguished by their good wet and light fastness properties.

The same colour salt is also obtained if the dyestufi obtained according to paragraph A is heated for 1 hour TABLE I N o. Diazo component Coupling component Shade n polyester fibres 1 4-amino-4-methylsulphony1azobenzene 2,3-dihydro-2-imino-3-methyl-benzthiazole Yellowish orange. 2 4-amino-4-nitroazobenzene 2,3-dihydro-2-imino-3-ethyl-6-ch1orobenzthiazole D0. 3 .d0 2,3-dihydro-2-imino-3-methyl-6-bromo-benzthiazole D0. 4 4-amino-2-methoxy-4-nitroazobenzene 2,3-dihydro-2-imino-3-methyl-G-methoxybenzthiazole Orange. 5 2-methy1-4-amin0-4-nitr0azobenzene 2,3-dihydro-2-imin0-3,6-dimethyl-benzthiaz0le Do. 6 4-amino-3-cyanoazobenzene 2,3-dihydr0-2-imino-3-ethyl-6-n1eth0xybenzthiazole D0. 7 2-methoxy-4-amin0-4-nitr0azobenzene- 2,3-dihydro-2-irnino-3-methyl-6-eth0xybenzthiazole Do. 8 4-amino-4-methylsulpl1onylaz0benzene 2,B-dihydro-2-imino-3-niethyl-methoxybenzthiazole Yellowish orange. 9 4-amino-4-nitroazobenzene 2,3-dihydro-2-imin0-3-methyl-6acetylaminobenzthiazole. Orange. 10 4-amin0az0benze11e 2,3-dihydro-2-imino-3-methylsulphonylbenzthiazole Yellowish orange.

(B) 4.9 parts of the dyestuif obtained according to paragraph A are mixed for minutes with 20 part of 20 charcoal has been added,

color salt is precipitated it is filtered. The yellow-orange with the aid of Zinc chloride and sodium chloride as the zinc chloride double salt. It has the formula The basic dyestuif so obtained dyes polyacrylonitrile fibers such as Acrilan under pressure at l00-110 in methanol with excess methyl iodide and the reaction mixture is worked up as above.

Similar cationic colour salts of the formula wherein A, B and Z have the meanings listed in the following table, are obtained by methylating the diazoimino compounds produced as described under (A) and precipitating the color as the zinc chloride double salt as described unfrom an acetic acid solution in der (B) Ex. No. A B Z 4-luethylsulfonylphenyl 1,4-phenylene 3-methyl-benzthiazolyl-(2)- 4-mtrophenyl d0 3-ethyl-6-chlor0benzthiazolyl-(2)- do I d n 3-methyl6-bromobenzthiaz0lyl- (2) 2-n ethoxy-4-mtrophenyl do 3-methyl-6-methoxybenzthiazolyl-(2)- 4n1trophenyl Z-methy 3,G-(limethylbenzthiazolyl-(2)- 3-cyanophenyl 4-nitrophenyl 4-methylsulfonyl phenyL. 4-m'tropheny1 PhenyllA-phenylne 2-meth yoxy-l ,4-phenylene 1,4-phenylene Example 65 (A) 19.7 parts of 4-aminoazobenzene are diazotised in the usual Way. The'clarified diazo solution is poured into a solution of 10.8 parts of 1,2-dihydro-l-methyl-2 iminopyridine in 300 parts of ice water which has been acidified with hydrochloric acid, the reaction mixture is neutralised by the gradual addition of sodium hydroxide Similar dyestulfs of the vformula are obtained by using equivalent amounts of the coupling component Z listed below with the alkylating agent listed in the following table under R and Y.

Ex. No. Z Alkylating agent R Y 66 1-methyl-pyridyl-(4) Diethy1sullate. OZH C H5S04-- 61 l-methyl-quinolinyl-(QZ) Dimethylsuliaten --CH3 21101 68 2-methyl-quinolinyl-(1) Methylbromide OH Brsolution and, on completion of the coupling, the yellow Example 69 triazene compound is filtered off, washed and dried. The product so obtained is a yellow powder of the formula v N G) CH3 I and this is worked up as described in paragraph B of Example l.

ll OH (A) a dispersion of 11.4 parts of 4-amino-4-methoxy azobenzene in a mixture of 200 parts of water, 20 parts of concentrated hydrochloric acid and 0.2 part of a dispersing agent is diazotised at room temperature with 3.9 parts of sodium nitrite in 20 parts of water. The clarified diazonium salt solution is poured into a hydrochloric acid solution of 8.0 parts of 2,3-dihydro-1,3-dimethyl-2- iminobenzimidazole and the reaction solution is carefully neutralised. After stirring for a longer time, the yellow triazene compound is filtered olf under suction and dried. It has the formula The coupling product of the above diazo component with 2,3-dihydro-1,2-dimethyl-3-iminoindazole is a similar product.

(B) 4.0 parts of the triazene compound obtained according to paragraph A are methylated with 10 parts of dimethyl sulphate by the process described in paragraph B of Example 1 andthe product is worked up as there described. The color salt so obtained dissolves in water with a reddish yellow colour. It has the formula Example 71 (A) A solution of 10.7 parts of 3-amino-4'-hydroxyazobenzene' is added dropwise While stirring vigorously to a mixture of 200 parts of water, 20 parts of concentrated I N 5 hydrochloric acid and 0.1 part of non-ionogemc dispersing @0139 agent such as, e.g. the condensation product of a higher fatty alcohol and more than equivalents of ethylene 3 N oxide. The suspension so obtained is diazotised at room 10 temperature in the usual way with 3.9 parts of sodium nitrate. The clarified diazoniurm salt solution is poured Colour Salts having Similar P perties are obtained by into an acetic acid solution of 11.5 parts of 2-amino-3- methylating or ethylating the other triazene compounds ethyl-6-methoxybenzthiazolium chloride in 200 parts of obtainable according to paragraph A of this example. water. The reaction mixture is neutralised by the dropwise addition of dilute sodium hydroxide solution where- Example 70 upon the dyestuif of the formula (A) The diazo solution prepared in the usual way S from 19.7 parts of 4-aminobenzene is poured, while stirring well, into a mixture of 18.0 parts of 2-amino-6- 1 a methoxy-benzthiazole, 100 parts of glacial acetic acid and 300 parts of finely crushed ice. The solution is care- N fully neutralised with sodium hydroxide solution while cooling, so that the pH of the reaction mixture finally is CZHE 7-7.5. After stirring a considerable time, the precipitated yellow triazene compound is filtered ofl? under sucbegms preplliltate' on 'completlon of the couphng.the tion, washed and dried. It corresponds to the formula yellow dlazolmmq compound 18 fi1.tere.d Off under washed neutral wlth water and dried in vacuo at 60-70 g N By replacing in the above example with otherwise the same procedure, instead of 10.7 parts of 3-amino-4-hy- 0 dr-oxyazobenzene, the equivalent amounts of 3-amino-3- OHaO- hydroxyazobenzene, 3-amino-4' methoxyazobenzene, 3-

S amino-3' methoxyaz-obenzene, '3-am-ino-2-methyl-4'-ac-" A suspension of 3.9 parts of this dyestuif in 10 parts etylaminobenzfa'ne 3'amino'?l'methyl'ly'hydroxyazoben' of dimethyl sulphate is heated for 5 minutes at 100. Zene or i methylfll bflroxybenzene are l While still Warm, the melt is taken up in 400 parts of (B).A mlxture of the dlazolmmlo compoupd obtamed Warm water, the solution is buffered with sodium acetate 'accordmg to paraglagh A a 10 Paris 'ofodlmethyl until it has an acetic acid reaction when, after the addi- Phat? are heatd Wlthm 10 minutes to 110 .and.kept for tion of a little animal charcoal, it is filtered. The orange minutes at this The melt while sun Warm colour salt is precipitated with the aid of zinc chloride 15 Worked up as descnbed m paragraph B of Example and sodium chloride. It is identical with the product 40 The yello'w'orange Color Salt so obtamed of the formula described in paragraph B of Example 1.

(B) 7.8 parts of the triazene produced according to 00113 paragraph A of the formula N 1 ZnClr 4o CH3 O-NN=N N=N 011,0

S dyes polyacrylonitrile fibers from an acetic acid bath in and 3.6 parts of most finely pulverised potassium caryellow'orange The dyeipgs are Very fasth bonate in 150 parts of ethylmethyl ketone are boiled for m dyestufi Pbtamed p'toluene sulphomc 30 minutes. A solution of 2.7 parts of dimethyl sulphate aold methyl ester mstead of dlmethyl Sulfatein 20 parts of ethyhnethyl ketone is then added dropwise Similar 0010f Salts of the formula and the whole is kept for another 30 minutes at the boil.

After cooling the reaction mixture, it is poured into a s 59 4000 parts of Water, the precipitate is filtered oif and 0CH3 Washed With Water until the filtrate has a neutral reaction. ATN=N B N=N O e The product is identical to that described in paragraph A R of Example 1.

4.0 parts of this monoalkylation product are heated 60 02115 for 5 minutes at 100 With 10 parts of dimethyl sulphate and the melt, While still Warm, is worked up analogously are obtainfid y using equivalent amounts of the Coupling to the process given in paragraph A. The orange colour v products obtained as described under (A) with the alkylat salt so obtained is identical with the quarternised end ing agent listed in the following table under R and the Product of p ph A. anion listed in column Y.

gig: A B Alkylating agent R Y ii Jt i$$ yi ti i %?i1 idi?t% ?i 851. iir fs di- 3-methoxy henyl c H ZnCl 2 1 ;113: 514 -acetyla.mino- Dimethylsuliate CH;, 01 (with NaCl) 76 3-methyl-4-hydroxypheny1 do d CH3 CH3SO4 77 2' methyl-4 hydr0xyphenyl. do Methylbromidmi. C a Bf i1 7 Example 78 The diazonium salt solution produced from 18 parts of 2-amino-6-methoxybenzthiazole, 200 parts of 95% acetic acid, 20 parts of concentrated sulphuric acid and nii CH I and brought into solution by the addition of 4000 parts of hot water. One further part of 80% acetic acid, 2 parts of sodium acetate and 4 parts of a condensation product of olein alcohol and mols of ethylene oxide are added and 100 parts of Orlon 42 are introduced. The bath is heated within minutes to 90, kept at this temperature for 10 minutes and dyeing is then performed at the boil for 1 hour. The dyebath is almost completely exhausted. The goods so treated are then soaped for 15 minutes at 80 in 5000 parts of water with the addition of a sulphonated fatty acid condensation product, rinsed and dried. The polyacrylonitrile fiber is dyed in pure orange shades of excellent fastness to washing and light.

We claim:

1. A water-soluble cationic dyestuff of the formula wherein 18 yl, nitro-phenyl, cyano-phenyl, lower alkyl-sulfonylphenyl, sulfamyl-phenyl, N-lower alkyl-substituted sulfamyl-phenyl, N-hydroxy-lower alkyl-su-bstituted sulfamyl-phenyl, N-l-ower alkoxy-lower alkyl-subtituted sul-famyhphcnyl lower alkoxy-carbonyltrosyl sulphuric ac1d, corresponding to 6.9 parts of sodium 5 nitrite, is poured at 0-S, while stirring, into the solution i i ;f fg g fjgz g of 21.1 part s of 4-N-methylammoazobenzene in 150 parts carbamaghenyl alkox flower alk of acetic acid. The sulphuric acid is buffeted by the addi- Substituted carba 1 h y y tion of sodium acetate and then the reaction mass is B is a divalent i? gg i g th stirred for 3 hours at room temperature when it is finally 10 ing of phenylene lower g z fif g z pouwd into a i of f The yellow dlammimo oxy-phenylene, chlor-o-phenylene and bromo-phenylcompound precipitates. It is filtered off under suctlon, we; washed with a great deal of water and dried in vacuo. 4.0 parts of the triazene so obtained are heated for 10 Z j igi g fiigg iii fisi 2 g zg g g gigi: minutes in 10 parts of pure dimethyl sulphate at 100 ll0 15 Selected from the group zonsisting of 1 and the procedure given in Example paragraph B is folazolyl (3) 1,3 thiaZQ1y1 (2) 1 3 4gthiadiazolyl (z) lowed. The color salt so obtained is identical with the indazolyl (3), imidazolyl (z) i;enzimidaz olyl (z) prod c described 111 paragraph B of Example pyridyl-(Z),pyridy1-(4), benzthiaz-olyl-(Z), quinolyl A similar product is obtained on U SIIIg the equivalent 20 (2), quino1y1 (4), iS0 quin-o1y1 (1) and pyrimidinYL amount of 4-ethylaminoazobenzene 1n the process de- (2), and wherein the N ,substituent scribed above. R is lower alkyl, and

Example 79 Y repgefients an uncoloured anion, the triazene group of sai yestutr being linked to B in one of the posi- Polyacrylonitrile fibers are dyed with the water soluble color salts produced according to the above examples as 25 Hons maa and para to the am budge u said dyestufi being free from saltaforming groups which 0.5 part of the dyestuff obtained according to Example dissociate acid in water. 1 paragraph B are pasted with 0.5 part of 80% acetic acid 2. The compound of the formula 8 "'9 011 0 (H13 7 /ON=NN-N=N OH 01 3. The compound of the formula O-N=NNN=N -SO2CH3 01 4. The compound of the formula 5. The compound of the formula 6. The compound of the formula References Cited by the Examiner UNITED STATES PATENTS 3,055,881 9/1962 Voltz et a1. 260- 

1. A WATER-SOLUBLE CATIONIC DYESTUFF OF THE FORMULA 